ES2335562A1 - Heteromolecular metal-humic (chelate) complexes - Google Patents
Heteromolecular metal-humic (chelate) complexes Download PDFInfo
- Publication number
- ES2335562A1 ES2335562A1 ES200800449A ES200800449A ES2335562A1 ES 2335562 A1 ES2335562 A1 ES 2335562A1 ES 200800449 A ES200800449 A ES 200800449A ES 200800449 A ES200800449 A ES 200800449A ES 2335562 A1 ES2335562 A1 ES 2335562A1
- Authority
- ES
- Spain
- Prior art keywords
- heteromolecular
- chelates
- humic
- molecule
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000013522 chelant Substances 0.000 title description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 62
- 239000002184 metal Substances 0.000 claims abstract description 62
- 239000004021 humic acid Substances 0.000 claims abstract description 49
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000000126 substance Substances 0.000 claims abstract description 17
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 82
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 23
- 230000015572 biosynthetic process Effects 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000011575 calcium Substances 0.000 claims description 14
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- 230000000694 effects Effects 0.000 claims description 12
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- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000208 phytotoxic Toxicity 0.000 description 1
- 230000000885 phytotoxic effect Effects 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000009291 secondary effect Effects 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 239000004296 sodium metabisulphite Substances 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 229960003080 taurine Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D9/00—Other inorganic fertilisers
- C05D9/02—Other inorganic fertilisers containing trace elements
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F11/00—Other organic fertilisers
- C05F11/02—Other organic fertilisers from peat, brown coal, and similar vegetable deposits
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G1/00—Mixtures of fertilisers belonging individually to different subclasses of C05
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Fertilizers (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
Complejos (quelatos) metálicos heteromoleculares de naturaleza húmica.Heteromolecular metal complexes (chelates) Humic nature.
La presente invención se refiere a mejoras de la patente principal P200700595 relativa a una nueva familia de quelatos/complejos naturales mediante la formación de quelatos heteromoleculares o mixtos formados por moléculas naturales con capacidad complejante o quelante de diferente estructura química pertenecientes a dos grupos o familias diferentes, y un oligoelemento de carácter metálico.The present invention relates to improvements of the main patent P200700595 relating to a new family of chelates / natural complexes by chelating heteromolecular or mixed formed by natural molecules with complexing or chelating capacity of different chemical structure belonging to two different groups or families, and a metal trace element.
La preparación de formulaciones especiales que permitan una liberación controlada de los constituyentes de la formulación junto con la protección de dichos constituyentes de la interacción con el medio para minimizar su degradación y optimizar su eficiencia es de enorme interés. Este hecho es especialmente patente en el campo de la nutrición de oligoelementos tanto en plantas como animales y humanos.The preparation of special formulations that allow a controlled release of the constituents of the formulation together with the protection of said constituents of the interaction with the environment to minimize its degradation and optimize Its efficiency is of enormous interest. This fact is especially patent in the field of trace element nutrition in both Plants like animals and humans.
Así, en el área de la nutrición vegetal, en el caso de las plantas cultivadas en suelos básicos y calizos, la rápida precipitación de los oligoelementos de carácter metálico principalmente hierro, cobre, manganeso, zinc, y cobalto, debido al pH alcalino y a la formación de sales insolubles como carbonatos, hace que la nutrición de estos oligoelementos tenga que realizarse mediante compuestos especiales - quelatos orgánicos - con la capacidad de proteger el oligoelemento de las reacciones de bloqueo de los suelos (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972). Estos quelatos están formados por moléculas sintéticas, siendo los quelatos de EDDHA, para el Fe (III), y los de EDTA para los otros oligoelementos, los más eficaces y utilizados (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972). Sin embargo, estos compuestos plantean problemas importantes:Thus, in the area of plant nutrition, in the case of plants grown in basic and limestone soils, the rapid precipitation of trace elements of a metallic nature mainly iron, copper, manganese, zinc, and cobalt, due to Alkaline pH and the formation of insoluble salts such as carbonates, makes the nutrition of these trace elements have to be done by special compounds - organic chelates - with the ability to protect the trace element from blocking reactions of soils (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972). These chelates they are formed by synthetic molecules, being the chelates of EDDHA, for Faith (III), and those of EDTA for others trace elements, the most effective and used (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972). However, these compounds pose important problems:
- \bullet?
- Desde un punto de vista nutricional la co-absorción por la raíz del quelato orgánico causa cambios metabólicos en las plantas que causan, a su vez, cambios importantes en la calidad del fruto (Bienfait, F., Garcia-Mina, JMª., Zamarreño, A Mª. 2004. Distribution and secondary effects of EDDHA in some vegetable species. Soil Sci. Plant Nutr., 50, 1103-110). From a point of view Nutritional co-absorption by the chelate root Organic causes metabolic changes in the plants they cause, at their instead, important changes in the quality of the fruit (Bienfait, F., Garcia-Mina, JMª., Zamarreño, A Mª. 2004 Distribution and secondary effects of EDDHA in some vegetable species. Soil Sci. Plant Nutr., 50, 1103-110).
- \bullet?
- Desde un punto de vista medioambiental, la baja o nula biodegradabilidad de los quelatos utilizados plantea importantes problemas de contaminación de suelos y aguas (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972). From a point of view environmental, low or no biodegradability of chelates used raises important problems of soil contamination and waters (Abadía, J., Álvarez-Fernandez, A., Rombola, A.D., Sanz, M., Tagliavini, M., Abadía, A., 2004. Technologies for the diagnosis and remediation of Fe deficiency. Soil Sci Plant Nutr 50, 965-972).
- \bullet?
- Desde un punto de vista de la eficacia del producto, la elevada solubilidad en agua del producto favorece la lixiviación y las pérdidas. From a point of view of the product efficiency, high water solubility of the product favors leaching and losses.
En el área de la nutrición de los animales y humanos, son necesarios compuestos especiales que mejoren o favorezcan la adecuada bioasimilación de los oligoelementos aportados. Este hecho es especialmente importante en rumiantes cuya actividad microbiológica implica la inmovilización de una concentración importante de los oligoelementos aportados al ser empleados por los microorganismos del rumiante. En la actualidad, estas formulaciones consisten principalmente en quelatos de los oligoelementos con aminoácidos y péptidos (Ashmead, H.D.1993. The roles of amino acid Chelates in Animal Nutrition. Noyes Publication. New Jersey, USA). Sin embargo el gran problema que presentan estos compuestos es la elevada biodegradabilidad de los aminoácidos, así como la reducida constante de estabilidad de los complejos que forman (Ashmead, H.D.1993. The roles of amino acid Chelates in Animal Nutrition. Noyes Publication. New Jersey, USA).In the area of animal nutrition and human, special compounds are needed that improve or promote adequate bioassimilation of trace elements contributed. This fact is especially important in ruminants whose microbiological activity involves the immobilization of a significant concentration of the trace elements contributed by being used by ruminant microorganisms. Nowadays, these formulations consist mainly of chelates of trace elements with amino acids and peptides (Ashmead, H.D. 1993. The roles of amino acid Chelates in Animal Nutrition. Noyes Publication. New Jersey, USA). However, the big problem with these compounds is the high biodegradability of amino acids as well as the reduced stability constant of the complexes that form (Ashmead, H.D. 1993. The roles of amino acid Chelates in Animal Nutrition Noyes Publication. New Jersey, USA).
La presente invención ofrece una solución a los problemas anteriormente planteados a partir de una formulación que contiene compuestos presentes en la naturaleza, inocuos para el medioambiente, capaces de proteger el oligoelemento de las reacciones de bloqueo en los suelos (formación de hidróxidos y carbonatos), y que facilita una liberación gradual que controla los fenómenos de lixiviación produciendo un efecto beneficioso sobre el desarrollo de la planta y que pretende así mismo, la protección, tanto en animales monogástricos como en humanos, de los oligoelementos aportados de su reacción en el intestino con compuestos que puedan provocar su precipitación (por ejemplo por la formación de fitatos) mediante la formulación de quelatos/complejos que mejoren su bioasimilación en el intestino.The present invention offers a solution to problems previously raised from a formulation that It contains compounds present in nature, harmless to environment, capable of protecting the trace element from blocking reactions in soils (formation of hydroxides and carbonates), and that facilitates a gradual release that controls the leaching phenomena producing a beneficial effect on the development of the plant and that also seeks protection in both monogastric and human animals, of contributed trace elements of your reaction in the intestine with compounds that may cause precipitation (for example by phytate formation) by formulating chelates / complexes that improve your bioassimilation in the intestine.
Se conocen en el estado de la técnica antecedentes similares pero que difieren sustancialmente en la solución presentada en la presente solicitud. La patente US6080220 describe la obtención de un complejo especial de ácido húmico-hierro y su uso en la corrección de la clorosis férrica. Este complejo describe el uso de pirofosfato para disminuir los procesos de agregación durante la preparación de los complejos.They are known in the state of the art similar background but that differ substantially in the solution presented in this application. US6080220 patent describes obtaining a special acid complex humic-iron and its use in the correction of iron chlorosis This complex describes the use of pyrophosphate for decrease aggregation processes during the preparation of complex.
La patente US 5354350 describe la obtención de un complejo ácido húmico-Fe(III) insoluble al agua y que es preparado en presencia de un fosfato inorgánico.US 5354350 describes the obtaining of an insoluble humic acid-Fe (III) complex to water and that is prepared in the presence of a phosphate inorganic.
La US 4786307 describe la preparación de micronutrientes quelados mediante la mezcla de ácidos fúlvicos con diferentes hidroxiácidos y ácidos análogos del EDTA. En la presente invención se excluyen los ácidos fúlvicos debido a dos razones fundamentales: (i) la baja estabilidad de los complejos/quelatos ácido fúlvico-metal hace que cuando se mezclan con hidroxiácidos con capacidad quelante se forme el complejo con el hidroxiácido y no el complejo mixto implicando al ácido fúlvico y al hidroxiácido; (ii) los ácidos fúlvicos son altamente degradables por los microorganismos, por lo que sus complejos no implican una protección de la degradación micróbica.US 4786307 describes the preparation of chelated micronutrients by mixing fulvic acids with different hydroxy acids and similar acids of EDTA. At the moment invention fulvic acids are excluded due to two reasons Fundamental: (i) the low stability of complexes / chelates fulvic acid-metal makes when mixed with hydroxy acids with chelating capacity form the complex with the hydroxy acid and not the mixed complex involving fulvic acid and hydroxy acid; (ii) fulvic acids are highly degradable by microorganisms, so their complexes do not imply protection from microbial degradation.
En la US 4425149 se describe la preparación de un agente quelante mediante la mezcla de leonardita (32%) con ácido cítrico (3%), ácido nítrico (1%) y metanol (64%). Este tratamiento de la leonardita en medio ácido alcohólico generará la extracción a partir de la leonardita de ácidos fúlvicos (Stevenson, F.J., 1994. Humus Chemistry, Second Edition, Wiley, New Cork)), por lo que el agente quelante final (una vez eliminado el metanol) estaría constituido por ácidos fúlvicos y ácido cítrico. Como se señala anteriormente la presente invención no considera los ácidos fúlvicos debido a la baja constante de estabilidad de sus complejos con metales y la alta susceptibilidad de ser atacado y degradado por los microorganismos.In US 4425149 the preparation of a chelating agent by mixing leonardite (32%) with acid citric (3%), nitric acid (1%) and methanol (64%). This treatment of the leonardite in alcoholic acid medium will generate the extraction to from leonardite of fulvic acids (Stevenson, F.J., 1994. Humus Chemistry, Second Edition, Wiley, New Cork)), so the final chelating agent (once methanol is removed) would be constituted by fulvic acids and citric acid. As noted previously the present invention does not consider fulvic acids due to the constant low stability of its complexes with metals and the high susceptibility of being attacked and degraded by microorganisms
La patente US 4698090 contempla un método de
extracción de sustancias húmicas a partir de leonardita mediante
reacción con diferentes sustancias incluyendo sales de ácidos
orgánicos. En esta patente en ningún caso se describe la formación
de complejos mixtos o heteromoleculares del tipo de los descritos en
la presente invención, ni se ajustan las condiciones de reacción
(principalmente estequiometría) para que se formen dichos complejos.
Igualmente, los elevados pH de reacción (altamente básicos)
descritos en esta patente impedirían la formación de los
complejos.US patent 4698090 contemplates a method of extracting humic substances from leonardite by reaction with different substances including salts of organic acids. In this patent, the formation of mixed or heteromolecular complexes of the type described in the present invention is not described, nor are the reaction conditions (mainly stoichiometry) adjusted so that said complexes are formed. Likewise, the high (highly basic) reaction pH described in this patent would prevent the formation of
complex.
Finalmente, la US 6649566 contempla la preparación de mezclas de sustancias húmicas con ácido salicílíco y quitosan, pero en ningún caso contemplan la formación de complejos de ácido húmico - metal - ácido salicílico, así como formulaciones de liberación gradual de ácido salicílico.Finally, US 6649566 contemplates the preparation of mixtures of humic substances with salicylic acid and chitosan, but in no case contemplate the formation of complexes of humic acid - metal - salicylic acid, as well as formulations gradual release of salicylic acid.
En este contexto, la presente invención se refiere a una nueva familia de quelatos/complejos naturales mediante la formación de quelatos heteromoleculares o mixtos formados por moléculas naturales con capacidad complejante o quelante de diferente estructura química pertenecientes a dos grupos o familias diferentes, y un oligolemento de carácter metálico. Como se ha señalado, estas moléculas orgánicas con capacidad complejante o quelante están agrupadas en dos familias. Una familia constituida por un ácido húmico (ácidos húmicos y sus fracciones: ácido húmico gris y ácido húmico marrón) o un sistema húmico conteniendo ácidos húmicos, y otra familia constituida por moléculas orgánicas multidentadas con capacidad complejante/quelante, como por ejemplo hidroxiácidos (cítrico, oxálico, succínico, málico ...); ácido ftalico, ácido salicílico, derivados del ácido acético, ácido glucónico y derivados, aminoácidos y péptidos, lignosulfonatos, azúcares, y aminas orgánicas.In this context, the present invention is refers to a new family of chelates / natural complexes by the formation of heteromolecular or mixed chelates formed by natural molecules with complexing or chelating capacity of different chemical structure belonging to two groups or families different, and a trace element of metallic character. How has it noted, these organic molecules with complexing capacity or Chelating are grouped into two families. An established family by a humic acid (humic acids and their fractions: humic acid gray and brown humic acid) or a humic system containing acids humic, and another family consisting of organic molecules multidentadas with complexing / chelating capacity, such as hydroxy acids (citric, oxalic, succinic, malic ...); acid phthalic, salicylic acid, acetic acid derivatives, acid gluconic and derivatives, amino acids and peptides, lignosulfonates, sugars, and organic amines.
Como elección preferente se utilizarán aquellas moléculas orgánicas multidentadas que formen complejos con el metal con una constante de estabilidad (log K) situada entre 2-20.The preferred choice will be those multidentate organic molecules that form complexes with metal with a stability constant (log K) located between 2-20.
De esta manera el complejo/quelato natural objeto de la invención tomaría la fórmula general:In this way the natural chelate / complex object of the invention would take the general formula:
[Sistema húmico]_{n} - (Metal)_{x} - [molécula orgánica multidentada]_{m}[System humic] n - (Metal) x - [organic molecule multi-intended] m
en la que los valores de n, x y m dependerán del número de coordinación del metal y de los grupos funcionales complejantes del sistema húmico y de la molécula orgánica multidentada.in which the values of n, x and m depend on the coordination number of the metal and the groups complexing functions of the humic system and the molecule organic multi-purpose
Estos complejos/quelatos heteromoleculares de naturaleza húmica poseen una geometría molecular que por un lado impide la formación de grandes agregados moleculares de baja solubilidad (problema clásico al intentar preparar complejos metálicos de ácido húmico), y también poseen alta estabilidad al satisfacerse todos los centros de coordinación del metal. Esta elevada estabilidad facilita la adecuada protección química del metal y de la molécula multidentada implicados en este tipo de complejo. Esta protección química impide la retrogradación del metal por la formación de sales insolubles con compuestos inorgánicos (por ejemplo, carbonatos, fosfatos, etc) o moléculas orgánicas (fitatos).These heteromolecular complexes / chelates of humic nature possess a molecular geometry that on the one hand prevents the formation of large molecular aggregates of low solubility (classic problem when trying to prepare complexes humic acid metal), and also have high stability to meet all metal coordination centers. This high stability facilitates the adequate chemical protection of the metal and multistained molecule involved in this type of complex. This chemical protection prevents the retrogradation of the metal by the formation of insoluble salts with inorganic compounds (by example, carbonates, phosphates, etc.) or organic molecules (phytates)
Igualmente la molécula húmica también dota al complejo de una protección microbiológica debido al efecto anti-microbiano de estas sustancias. De esta manera estos complejos/quelatos objeto de la invención protegerían al metal y a la molécula multidentada de los fenómenos de degradación debido al ataque de microorganismos. Igualmente, en el caso de su aplicación en suelos, la capacidad de fijación de los sistemas húmicos en arcillas y constituyentes del suelo facilitaran su implantación en la rizosfera y el control de los fenómenos de lixiviación. También, el carácter natural de las moléculas implicadas en el complejo minimiza los riesgos medioambientales.Likewise, the humic molecule also provides complex of a microbiological protection due to the effect Anti-microbial of these substances. In this way these complexes / chelates object of the invention would protect the metal and to the multidented molecule of degradation phenomena due to to the attack of microorganisms. Likewise, in the case of your application in floors, the fixing capacity of the systems humic in clays and soil constituents will facilitate their implantation in the rhizosphere and the control of the phenomena of leaching Also, the natural character of the molecules involved in the complex minimizes environmental risks.
Igualmente, como se ha señalado, los complejos (quelatos) heteromoleculares descritos en la presente invención implican la protección de la molécula orgánica multidentada empleada en su preparación. Una aplicación muy útil de esta propiedad es por ejemplo la preparación de un complejo del tipo ácido húmico-Fe(III)-ácido salicílico con el fin de proporcionar gradualmente ácido salicílico a las plantas. Es sabido que el ácido salicílico es un efectivo estimulante del sistema defensivo de las plantas además de tener otras propiedades anti-estrés. Sin embargo el reducido margen existente entre el intervalo de dosis eficaces y el correspondiente a las dosis fitotóxicas hace que su empleo sea muy complicado. Con el complejo heteromolecular descrito del tipo de los considerados en la presente invención, se conseguirían tres efectos complementarios que se expresarían a medida que el complejo es hidrolizado en la rizosfera en su interacción con la raíz de la planta:Likewise, as noted, the complexes heteromolecular (chelates) described in the present invention involve the protection of the multidented organic molecule used In its preparation. A very useful application of this property is by example the preparation of an acid type complex humic-Fe (III) -salicylic acid in order to gradually provide salicylic acid to plants. Is known that salicylic acid is an effective system stimulant defensive of plants in addition to having other properties anti-stress. However the small margin between the effective dose range and the corresponding one at phytotoxic doses makes its use very complicated. With the described heteromolecular complex of the type considered in the present invention, three complementary effects would be achieved that would be expressed as the complex is hydrolyzed in the Rhizosphere in its interaction with the root of the plant:
- \bullet?
- Una formulación de liberación gradual de ácido salicílico libre a la rizosfera. A release formulation Gradual free salicylic acid to the rhizosphere.
- \bullet?
- Una formulación conteniendo Fe asimilable A formulation containing Fe assimilable
- \bullet?
- El efecto estimulante del ácido húmico libre. The acid stimulating effect Humic free.
El mecanismo de hidrólisis del complejo heteromolecular ácido húmico-Fe(III)-ácido cítrico en la rizosfera comienza por la interacción del complejo con el sistema quelato-reductasa en la superficie de la raíz. Este proceso conlleva la hidrólisis del complejo y la reducción del Fe(III) a Fe(II) que es posteriormente transportado al interior de la raíz. Este proceso liberaría al ácido húmico y a la molécula orgánica multidentada, en este caso al ácido cítrico.The mechanism of hydrolysis of the complex heteromolecular humic acid-Fe (III) -acid citrus in the rhizosphere begins with the interaction of the complex with the chelate-reductase system on the surface of the root. This process involves the hydrolysis of the complex and the reduction of Fe (III) to Fe (II) which is subsequently transported inside the root. This process would release the acid humic and the multidented organic molecule, in this case acid citric.
Hay que decir que estos efectos se han observado cuando los ácidos húmicos están implicados en el proceso, pero no se han observado con los ácidos fúlvicos. Este hecho es causado por dos razones principales: (i) los ácidos fúlvicos son altamente biodegradables por los microorganismos; (ii) la constante de estabilidad de los complejos ácido fúlvico-metal son sensiblemente inferiores a las del correspondiente ácido húmico-metal, y debido a este hecho no se llegan a formar los complejos heteromoleculares objeto de la invención.It must be said that these effects have been observed when humic acids are involved in the process, but do not know have observed with fulvic acids. This fact is caused by two main reasons: (i) fulvic acids are highly biodegradable by microorganisms; (ii) the constant of stability of the fulvic acid-metal complexes are significantly lower than the corresponding acid humic-metal, and due to this fact they do not reach form the heteromolecular complexes object of the invention.
En definitiva, en esta invención se describe la preparación y uso de un nuevo tipo de complejos consistente en una familia de complejos (quelatos) heteromoleculares de naturaleza húmica cuya estabilidad biológica y química permite la protección del metal y de la molécula multidentada implicados en el complejo de los fenómenos de degradación tanto por vía química como microbiológica. Además, en todos los casos, se tiene el efecto beneficioso del sistema húmico, tanto como efectivo estimulante del crecimiento y nutrición de las plantas; como activador metabólico y del sistema inmunológico de animales y humanos.In short, this invention describes the preparation and use of a new type of complex consisting of a family of heteromolecular complexes (chelates) of nature humic whose biological and chemical stability allows protection of the metal and multistained molecule involved in the complex of degradation phenomena both chemically and microbiological In addition, in all cases, it has the effect beneficial of the humic system, as well as effective stimulant of the plant growth and nutrition; as metabolic activator and of the immune system of animals and humans.
Así en la presente invención se describe el uso y preparación de complejos orgánicos metálicos heteromoleculares o mixtos del tipo descrito en la formula general siguiente:Thus in the present invention the use is described and preparation of heteromolecular metal organic complexes or mixed of the type described in the following general formula:
(A)n - (Metal)x - (B)m(A) n - (Metal) x - (B) m
en la que A es uno o varios compuestos húmicos del tipo ácido húmico o cualquiera de sus fracciones (ácido húmico gris o marrón), o un sistema húmico conteniendo ácidos húmicos, y B es un (o varios) compuesto complejante (quelante orgánico) no húmico, una molécula orgánica multidentada, como por ejemplo hidroxiácidos (cítrico, oxálico, succínico, málico ...); ácido ftalico, ácido salicílico, derivados del ácido acético, ácido glucónico y derivados, aminoácidos y péptidos, lignosulfonatos, azúcares, y aminas orgánicas.in which A is one or several humic compounds of the humic acid type or any of its fractions (gray or brown humic acid), or a humic system containing humic acids, and B is a (or several) compound complexing (organic chelator) non humic, an organic molecule multidented, such as hydroxy acids (citric, oxalic, succinic, malic ...); phthalic acid, salicylic acid, derivatives of acetic acid, gluconic acid and derivatives, amino acids and peptides, lignosulfonates, sugars, and amines organic.
La molécula orgánica multidentada puede ser cualquiera aunque preferentemente se utilizarán aquellas que presentan una constante de estabilidad (log K) del complejo (quelato) molécula B (molécula orgánica multidentada) - metal comprendida entre 2 y 20.The multidentate organic molecule can be any but preferably those that have a stability constant (log K) of the complex (chelate) molecule B (multistained organic molecule) - metal between 2 and 20.
M puede ser cualquier metal (o varios metales), en cualquiera de sus estados de oxidación, como por ejemplo Fe (II,III), Mn, Cu, Zn, Co, Ti, Mo, B y Se.M can be any metal (or several metals), in any of its oxidation states, such as Fe (II, III), Mn, Cu, Zn, Co, Ti, Mo, B and Se.
En todos los casos la formación del enlace B-Metal junto con la formación del enlace A-Metal conlleva la inhibición de la formación del enlace A-Metal-A que conllevaría los procesos de agregación molecular.In all cases the link formation B-Metal together with link formation A-Metal entails the inhibition of the formation of A-Metal-A link that would entail molecular aggregation processes.
Los ácidos húmicos o/y los sistemas húmicos
completos conteniendo ácidos húmicos se pueden extraer de uno o
varios materiales orgánicos sedimentarios (como por ejemplo,
lignitos, leonarditas, turbas, ...) o materiales vegetales
compostados, que pueden estar tratados previamente con cualquier
tratamiento químico o biológico orientado a incrementar la
concentración de ácidos húmicos o variar su estructura (tratamientos
de oxidación, hidro-
genación, ...). También los ácidos
húmicos o/y los sistemas húmicos completos conteniendo ácidos
húmicos se pueden obtener mediante síntesis química o/y enzimática a
partir de precursores orgánicos.Humic acids or / and complete humic systems containing humic acids can be extracted from one or several sedimentary organic materials (such as lignites, leonardites, mobs, ...) or composted plant materials, which can be previously treated with any chemical or biological treatment aimed at increasing the concentration of humic acids or varying their structure (oxidation treatments, hydro-
genación, ...). Also humic acids or / and complete humic systems containing humic acids can be obtained by chemical or / and enzymatic synthesis from organic precursors.
Igualmente se pueden utilizar ácidos húmicos o cualquiera de sus fracciones como por ejemplo el ácido húmico gris o marrón.You can also use humic acids or any of its fractions such as gray humic acid or Brown.
En todos los casos estos complejos heteromoleculares objeto de la invención se pueden formular junto con uno o varios nutrientes minerales (como por ejemplo, nitrógeno, potasio y fósforo) y uno o varios compuestos bioestimulantes de las plantas como por ejemplo, azucares, oligosacáridos, polisacáridos (por ejemplo quitosan), auxinas (ácido indol-acético y derivados, indol, triptófano), citoquininas (zeatina y derivados, isopentiladenina y derivados, isopentiladenosina y derivados, adenosina, adenina, isopentil-alcohol, ...), giberelinas, etileno o precursores del etileno, poliaminas, óxido nítrico o precursores-dadores de óxido nítrico, nucleóticos cíclicos o compuestos con la capacidad de incrementar la concentración intracelular de nucleótidos cíclicos, aminoácidos, brasinoesteriodes, salicilatos, otras sustancias húmicas, y lignosulfonatos.In all cases these complexes Heteromolecular objects of the invention can be formulated together with one or more mineral nutrients (such as nitrogen, potassium and phosphorus) and one or more biostimulant compounds of the plants such as sugars, oligosaccharides, polysaccharides (eg chitosan), auxins (indole acetic acid and derivatives, indole, tryptophan), cytokinins (zeatin and derivatives, isopentyladenine and derivatives, isopentyladenosine and derivatives, adenosine, adenine, isopentyl alcohol, ...), gibberellins, ethylene or ethylene precursors, polyamines, oxide nitric or nitric oxide precursor-donors, cyclic nucleotides or compounds with the ability to increase the intracellular concentration of cyclic nucleotides, amino acids, Brasinosteriodes, salicylates, other humic substances, and lignosulfonates.
En todos los casos estos complejos heteromoleculares objeto de la invención se pueden formular junto con uno o varios nutrientes minerales (como por ejemplo, nitrógeno, potasio, fósforo, calcio y magnesio) y uno o varios compuestos bioestimulantes del sistema metabólico e inmunitario de animales y seres humanos como por ejemplo, oligosacáridos, azucares, vitaminas y cualquier compuesto de síntesis con efecto sobre la salud y el aprovechamiento del alimento.In all cases these complexes Heteromolecular objects of the invention can be formulated together with one or more mineral nutrients (such as nitrogen, potassium, phosphorus, calcium and magnesium) and one or more compounds biostimulants of the animal's metabolic and immune system and humans such as oligosaccharides, sugars, vitamins and any synthetic compound with effect on health and Food utilization.
La mejora introducida en esta adición a la patente P200700595 consiste en que el ácido húmico se puede tratar en procesos de transformación y se ha comprobado que algunos de estos procesos afectan directamente a la solubilidad del complejo que constituye el producto final, más concretamente a su solubilidad a fuerzas iónicas elevadas o en presencia de cationes polivalentes como el Ca^{++}.The improvement introduced in this addition to the P200700595 patent is that humic acid can be treated in transformation processes and it has been proven that some of these processes directly affect the solubility of the complex which constitutes the final product, more specifically its solubility at high ionic forces or in the presence of polyvalent cations as the Ca ++.
Se ha comprobado que la solubilidad de los
complejos objeto de la invención aumenta de forma muy significativa
cuando el ácido húmico (o los ácidos húmicos) utilizado en la
formación del complejo hetero-nuclear descrito en la
patente P200700595, está total o parcialmente sulfonado. También se
consigue dicho efecto de aumento de la solubilidad cuando dicho
ácido húmico (o los ácidos húmicos) ha sido tratado con una amina en
una etapa posterior a la formación del complejo
hetero-nuclear, con el fin de proteger los grupos
carboxílicos de la interacción con los cationes polivalentes.
También se ha observado que se incrementa la solubilidad cuando se
aumenta la acidez del ácido húmico (presencia de grupos ácidos y/o
fenólicos) mediante cualquier tipo de tratamiento químico o
físico.It has been found that the solubility of the complexes object of the invention increases significantly when the humic acid (or humic acids) used in the formation of the hetero-nuclear complex described in the P200700595 patent, is totally or partially sulphonated. Said solubility increase effect is also achieved when said humic acid (or humic acids) has been treated with an amine at a stage subsequent to the formation of the hetero-nuclear complex, in order to protect the carboxylic groups from interaction. with polyvalent cations. It has also been observed that solubility is increased when the acidity of humic acid (presence of acidic and / or phenolic groups) is increased by any type of chemical treatment or
physical.
El aumento de la solubilidad del complejo hetero-nuclear en aguas ricas en calcio, se ha conseguido tratado dicho complejo con cualquier producto secuestrante de calcio, como podrían ser quelatos de síntesis EDTA, NTA, productos inorgánicos como polifosfatos o moléculas orgánicas o inorgánicas que contienen fósforo.The increase in the solubility of the complex hetero-nuclear in calcium-rich waters, it has got treated said complex with any product calcium sequestrant, such as EDTA synthesis chelates, NTA, inorganic products such as polyphosphates or organic molecules or inorganic containing phosphorus.
En relación con el proceso de sulfonación de los ácidos húmicos, este debe ser realizado antes de formar el complejo hetero-nuclear, y se puede realizar utilizando cualquiera de los métodos conocidos como son: el tratamiento con ácido sulfúrico concentrado en ausencia o presencia de piridina, el tratamiento con ácido cloro-sulfónico, el tratamiento de oxidación con meta-bisulfito, etc...In relation to the sulfonation process of humic acids, this must be done before forming the complex hetero-nuclear, and can be done using Any of the methods known as are: treatment with concentrated sulfuric acid in the absence or presence of pyridine, the treatment with chloro-sulphonic acid, the oxidation treatment with meta-bisulfite, etc...
En relación con el proceso de protección de los grupos carboxílicos libres se puede realizar por reacción del complejo hetero-nuclear una vez formado con una amina tal como la etanolamina, la glucosamina, la taurina, etc...In relation to the process of protection of Free carboxylic groups can be performed by reacting the hetero-nuclear complex once formed with a amine such as ethanolamine, glucosamine, taurine, etc...
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El producto se puede obtener vía sólida o vía líquida, o empleando algunos de los componentes en fase sólida o en disolución:The product can be obtained via solid or via liquid, or using some of the components in solid phase or in dissolution:
Se describen tres diferentes métodos de fabricación por orden preferente:Three different methods of Manufacturing by preferred order:
Método 1Method one
Básicamente consiste en la preparación del complejo B-Metal, y la posterior adición de este complejo sobre el componente A (el ácido húmico) en unas condiciones de pH, presión y temperatura preferentes.It basically involves the preparation of B-Metal complex, and the subsequent addition of this complex on component A (humic acid) under conditions of preferred pH, pressure and temperature.
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Método 2Method 2
Básicamente consiste en la adición del componente conteniendo el metal sobre el componente conteniendo las moléculas A y B (componente AB) en unas condiciones de pH, presión y temperatura preferentes.It basically involves the addition of component containing the metal on the component containing the molecules A and B (component AB) under conditions of pH, pressure and Preferred temperature
(cabe la posibilidad de adicionar el componente AB sobre el componente metal, pero es mucho menos eficaz).(It is possible to add the AB component over the metal component, but it is much less effective).
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Método 3Method 3
Básicamente consiste en la preparación del complejo A-Metal y la adición posterior del componente contenido B en unas condiciones de pH, presión y temperatura preferentes..It basically involves the preparation of A-Metal complex and the subsequent addition of B content component under conditions of pH, pressure and preferred temperature ..
Como hemos señalado se pueden preparar mezclas de complejos mixtos heteromoleculares del tipo de los descritos en la invención, utilizando en la reacción varios metales mezclados, vahos compuestos de la clase B mezclados y varios compuestos de la clase A mezclados.As we have indicated, mixtures can be prepared of heteromolecular mixed complexes of the type described in the invention, using various mixed metals in the reaction, mixed compounds of class B mixed and various compounds of the Class A mixed.
La vía preferente de preparación es por vía líquida, para la obtención de un producto líquido que puede ser utilizado directamente o en fase sólida previo secado o liofilizado.The preferred preparation route is via liquid, to obtain a liquid product that can be used directly or in solid phase prior to drying or lyophilized
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Las condiciones de reacción son:The reaction conditions are:
En fase líquida (todos los componentes a algún componente este en fase líquida) puede ser cualquier valor de pH, presión y temperatura aunque las condiciones preferentes son:In liquid phase (all components to some component in liquid phase) can be any pH value, pressure and temperature although the preferred conditions are:
- \bullet?
- El pH: entre 7 y 10. The pH: between 7 and 10.
- \bullet?
- La temperatura: entre 25 y 80ºC. The temperature: between 25 and 80 ° C
- \bullet?
- La presión: entre 1-2 atmósferas de presión. The pressure: between 1-2 atmospheres of pressure.
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En fase sólida, puede ser cualquier valor de pH, presión y temperatura aunque las condiciones preferentes son:In solid phase, it can be any pH value, pressure and temperature although the preferred conditions are:
- \bullet?
- El pH: entre 7 y 10. The pH: between 7 and 10.
- \bullet?
- La temperatura: entre 25 y 120ºC. The temperature: between 25 and 120 ° C.
- \bullet?
- La presión: entre 1-10 atmósferas de presión. The pressure: between 1-10 atmospheres of pressure.
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- La presentación puede ser sólida (granulado, pellets o polvo) o líquida.The presentation can be solid (granulated, pellets or powder) or liquid
- --
- En plantas, el modo de aplicación puede ser en fertirrigación (en la solución de riego) o directamente, inyectándolo al suelo o a la planta. También se puede aplicar el sólido o el líquido al pie de la planta o en aplicación foliar.In plants, the mode of application can be in fertirrigation (in the irrigation solution) or directly, injecting it into the soil or plant. The solid or liquid can also be applied to the foot of the plant or foliar application.
- --
- En animales o seres humanos se pueden aplicar sólidos mezclados o no con el alimento diario, o en forma líquida, por ejemplo diluido en el agua de bebida.In animals or humans can be applied mixed solids or not with daily food, or in liquid form, for example diluted in drinking water
- --
- En el caso de las plantas, y en la corrección de carencias en metales, las dosis se expresan en peso de metal complejado por hectárea o planta.At In the case of plants, and in the correction of metal deficiencies, doses are expressed in weight of complexed metal per hectare or plant.
- --
- Evidentemente, la dosis varía en función del cultivo y el metal considerado. Así, hablando de Fe y expresado por hectárea, la dosis óptima sería:Obviously, the dose varies depending on of the crop and the metal considered. Thus, speaking of Faith and expressed per hectare, the optimal dose would be:
- --
- En aplicación foliar, entre 0.3 y 0.8 kg de Fe complejado/haIn foliar application, between 0.3 and 0.8 kg of complexed Fe / ha
- --
- En aplicación a suelo, entre 3 y 6 kg de Fe complejado/haIn application to soil, between 3 and 6 kg of Fe complexed / ha
- --
- En el caso de plantas, y en el caso de una formulación destinada al aporte gradual (liberación gradual) de una o varias moléculas orgánicas implicadas en el complejo (como por ejemplo el ácido salicílico), las dosis se adaptarán a la dosis óptima de actuación de la molécula orgánica implicada en el complejo y que se libera gradualmente.At case of plants, and in the case of a formulation intended for contribution gradual (gradual release) of one or more organic molecules involved in the complex (such as salicylic acid), the doses will adapt to the optimal dose of the molecule organic implicated in the complex and released gradually.
- --
- En el caso de los animales y humanos las dosis se adaptarán a las necesidades diarias en el oligoelemento complejado, o a las dosis óptimas de actuación de la molécula orgánica multidentada o del ácido húmico.At In the case of animals and humans, the doses will be adapted to the daily needs in the complexed trace element, or at doses optimal performance of the multidented organic molecule or the humic acid
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Ejemplo 1Example one
Etapa 1Stage one
Se hace reaccionar en medio acuoso por cada mol de ácido cítrico, 3 moles de hierro y 14 moles de amoniaco. El producto sólido que se obtiene mediante secado posee un 28% de hierro como citrato de hierro amoniacal.It is reacted in aqueous medium for each mole of citric acid, 3 moles of iron and 14 moles of ammonia. He solid product obtained by drying has 28% of iron as ammoniacal iron citrate.
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Etapa 2Stage 2
Se mezclan a partes iguales, con agitación constante, dos disoluciones: A, una disolución de citrato de hierro amoniacal al 5,6% de hierro, y B, una disolución de 14% de humato potásico. El pH de reacción se ajusta a 9. La reacción se hace a 25ºC y 1 atmósfera de presión. Después de 4 horas de reacción, el producto resultante contiene un 2,8% de hierro complejado (quelatado) por el sistema heteromolecular humato-citrato.Mix in equal parts, with stirring constant, two solutions: A, a solution of iron citrate 5.6% ammoniacal iron, and B, a 14% solution of humate potassium The reaction pH is adjusted to 9. The reaction is done at 25 ° C and 1 atmosphere of pressure. After 4 hours of reaction, the resulting product contains 2.8% complexed iron (chelated) by the heteromolecular system Humate citrate.
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Ejemplo 2Example 2
Etapa 1Stage one
Se hace reaccionar en medio acuoso por cada mol de ácido salicílico, 1 mol de hierro y 8 moles de amoniaco. El producto que se obtiene contendría el salicilato de hierro. Este producto se puede secar o utilizar en fase líquida.It is reacted in aqueous medium for each mole of salicylic acid, 1 mole of iron and 8 moles of ammonia. He product obtained would contain iron salicylate. This Product can be dried or used in liquid phase.
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Etapa 2Stage 2
Se mezclan a partes iguales, con agitación constante, dos disoluciones: A, una disolución de salicilato de hierro amoniacal al 5,6% de hierro, y B, una disolución de 14% de humato potásico. El pH de reacción se ajusta a 9. La reacción se hace a 25ºC y 1 atmósfera de presión. Después de 4 horas de reacción, el producto resultante contiene un 2,8% de hierro complejado (quelatado) por el sistema heteromolecular humato-salicilato.Mix in equal parts, with stirring constant, two solutions: A, a salicylate solution of 5.6% ammoniacal iron, and B, a 14% solution of potassium humate The reaction pH is adjusted to 9. The reaction is makes at 25 ° C and 1 atmosphere of pressure. After 4 hours of reaction, the resulting product contains 2.8% iron complexed (chelated) by the heteromolecular system humate salicylate.
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Ejemplo 3Example 3
Etapa 1Stage one
Se hace reaccionar en medio acuoso por cada mol de ácido cítrico y de ácido oxálico, 3 y 2 moles de hierro respectivamente y 14 y 11 moles de amoniaco respectivamente. El producto sólido que se obtiene mediante secado, posee un 28% de hierro como una mezcla de complejos citrato y oxalato de hierro amoniacal.It is reacted in aqueous medium for each mole of citric acid and oxalic acid, 3 and 2 moles of iron respectively and 14 and 11 moles of ammonia respectively. He solid product that is obtained by drying, has 28% of iron as a mixture of citrate and iron oxalate complexes ammoniacal
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Etapa 2Stage 2
Se mezclan a partes iguales, con agitación constante, dos disoluciones: A, una disolución de citrato/oxalato de hierro amoniacal al 5,6% de hierro, y B, una disolución de 14% de humato potásico. El pH de reacción se ajusta a 9. La reacción se hace a 25ºC y 1 atmósfera de presión. Después de 4 horas de reacción, el producto resultante contiene un 2,8% de hierro complejado (quelatado) por el sistema heteromolecular humato-citrato y humato-oxalato.Mix in equal parts, with stirring constant, two solutions: A, a citrate / oxalate solution of 5.6% ammoniacal iron, and B, a 14% solution of potassium humate The reaction pH is adjusted to 9. The reaction is makes at 25 ° C and 1 atmosphere of pressure. After 4 hours of reaction, the resulting product contains 2.8% iron complexed (chelated) by the heteromolecular system humate-citrate and humate-oxalate.
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Ejemplo 4Example 4
Etapa 1Stage one
Se hace reaccionar en medio acuoso por cada mol de ácido cítrico, 3 moles de hierro/manganeso/zinc y 14 moles de amoniaco. El producto sólido que se obtiene posee un 28% de hierro/manganeso/zinc como citrato de hierro/manganeso/zinc amoniacal.It is reacted in aqueous medium for each mole of citric acid, 3 moles of iron / manganese / zinc and 14 moles of ammonia. The solid product obtained has 28% of iron / manganese / zinc as iron citrate / manganese / zinc ammoniacal
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Etapa 2Stage 2
Se mezclan a partes iguales, con agitación
constante, dos disoluciones: A, una disolución de citrato de
hierro/man-
ganeso/zinc amoniacal al 5,6% de
hierro/manganeso/zinc, y B, una disolución de 14% de humato de
potasio. El pH de reacción se ajusta a 9. La reacción se hace a 25ºC
y 1 atmósfera de presión. Después de 4 horas de reacción, el
producto resultante contiene un 2,8% de hierro/manganeso/zinc
complejados (quelatados) por el sistema heteromolecular
humato-citrato.Two solutions are mixed in equal parts, with constant stirring: A, a solution of iron citrate / handle
5.6% ammoniacal iron / manganese / zinc / zinc, and B, a 14% solution of potassium humate. The reaction pH is adjusted to 9. The reaction is done at 25 ° C and 1 atmosphere of pressure. After 4 hours of reaction, the resulting product contains 2.8% iron / manganese / zinc complexed (chelated) by the hemato-molecular humate-citrate system.
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Ejemplo 5Example 5
Etapa 1Stage one
En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 200 kg Humato potásico200 kg Potassium humate
- --
- 60 kg Meta-bisulfito sódico60 kg Sodium metabisulphite
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 605 litros de agua605 liters of water
Se mantiene la mezcla durante 24 horas a 85ºC. Una vez terminada la reacción se separan los sólidos por decantación durante 6 h. Mientras se deja enfriar la reacción.The mixture is maintained for 24 hours at 85 ° C. Once the reaction is over, the solids are separated by decantation for 6 h. While allowing the reaction to cool.
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Etapa 2Stage 2
- --
- Al producto anterior conteniendo los ácidos húmicos oxidados y sulfonados se le añaden despacio 125 kg de citrato de hierro (III).To the previous product containing oxidized humic acids and sulphonates are slowly added 125 kg of iron citrate (III).
- --
- Se mantiene agitando a temperatura ambiente durante 6 hBe keep stirring at room temperature for 6 h
- --
- El producto final se deja decantar durante 6 h antes de envasar.He final product is left to decant for 6 h before package.
Los productos obtenidos según se describe son menos sensibles a la precipitación en presencia de cationes polivalentes como Ca^{++}, Mg^{++} y otros.The products obtained as described are less sensitive to precipitation in the presence of cations polyvalents such as Ca ++, Mg ++ and others.
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Ejemplo 6Example 6
Etapa 1Stage one
- --
- En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 250 kg Humato potásico250 kg Potassium humate
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 500 litros de agua500 liters of water
Se mantiene la mezcla con agitación durante 4 h a temperatura ambiente.The mixture is kept under stirring for 4 h. at room temperature.
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Etapa 2Stage 2
Al producto anterior se añaden 125 kg de citrato de hierro (III). Se mantiene 6 h con agitación a temperatura ambiente.To the previous product 125 kg of citrate are added of iron (III). It is maintained 6 h with stirring at temperature ambient.
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Etapa 3Stage 3
Al producto anterior se añaden 50 kg de Glucosamina. Se mantiene agitando durante 6 h. Después se decanta y se envasa.To the previous product 50 kg of Glucosamine It is kept stirring for 6 h. Then he opts and It is packaged.
Los productos obtenidos según se describe son menos sensibles a la precipitación en presencia de cationes polivalentes como Ca^{++}, Mg^{++} y otros.The products obtained as described are less sensitive to precipitation in the presence of cations polyvalents such as Ca ++, Mg ++ and others.
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Ejemplo 7Example 7
Etapa 1Stage one
- --
- En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 250 kg Humato potásico250 kg Potassium humate
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 500 litros de agua500 liters of water
Se mantiene la mezcla con agitación durante 4 h a temperatura ambiente.The mixture is kept under stirring for 4 h. at room temperature.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Etapa 2Stage 2
Al producto anterior se añaden 125 kg de citrato de hierro (III). Se mantiene 6 h con agitación a temperatura ambiente.To the previous product 125 kg of citrate are added of iron (III). It is maintained 6 h with stirring at temperature ambient.
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Etapa 3Stage 3
Al producto anterior se añaden 50 kg de ácido heptaglucónico. Se mantiene agitando durante 6 h. Después se decanta y se envasa.50 kg of acid are added to the previous product Heptagluconic It is kept stirring for 6 h. Then he opts And it is packaged.
Los productos obtenidos según se describe son menos sensibles a la precipitación en presencia de cationes polivalentes como Ca^{++}, Mg^{++} y otros.The products obtained as described are less sensitive to precipitation in the presence of cations polyvalents such as Ca ++, Mg ++ and others.
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Ejemplo 8Example 8
Etapa 1Stage one
- --
- En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 250 kg Humato potásico250 kg Potassium humate
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 500 litros de agua500 liters of water
Se mantiene la mezcla con agitación durante 4 h a temperatura ambiente.The mixture is kept under stirring for 4 h. at room temperature.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Etapa 2Stage 2
Al producto anterior se añaden 125 kg de citrato de hierro (III). Se mantiene 6 h con agitación a temperatura ambiente.To the previous product 125 kg of citrate are added of iron (III). It is maintained 6 h with stirring at temperature ambient.
\newpage\ newpage
Etapa 3Stage 3
Al producto anterior se añaden 50 kg de fosfonato sódico. Se mantiene agitando durante 6 h. Después se decanta y se envasa.To the previous product 50 kg of sodium phosphonate It is kept stirring for 6 h. Later decants and is packaged.
Los productos obtenidos según se describe son menos sensibles a la precipitación en presencia de cationes polivalentes como Ca^{++}, Mg^{++} y otros.The products obtained as described are less sensitive to precipitation in the presence of cations polyvalents such as Ca ++, Mg ++ and others.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Ejemplo 9Example 9
Etapa 1Stage one
- --
- En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 250 kg Humato potásico250 kg Potassium humate
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 500 litros de agua500 liters of water
Se mantiene la mezcla con agitación durante 4 h a temperatura ambiente.The mixture is kept under stirring for 4 h. at room temperature.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Etapa 2Stage 2
Al producto anterior se añaden 125 kg de citrato de hierro (III). Se mantiene 6 h con agitación a temperatura ambiente.To the previous product 125 kg of citrate are added of iron (III). It is maintained 6 h with stirring at temperature ambient.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Etapa 3Stage 3
Al producto anterior se añaden 50 kg de EDTA. Se mantiene agitando durante 6h. Después se decanta y se envasa.50 kg of EDTA is added to the previous product. Be Keep stirring for 6h. Then it is decanted and packaged.
Los productos obtenidos según se describe son menos sensibles a la precipitación en presencia de cationes polivalentes como Ca^{++}, Mg^{++} y otros.The products obtained as described are less sensitive to precipitation in the presence of cations polyvalents such as Ca ++, Mg ++ and others.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Ejemplo 10Example 10
Etapa 1Stage one
En un tanque-reactor con agitador se añaden:In a tank-reactor with agitator are added:
- --
- 200 kg Humato potásico200 kg Potassium humate
- --
- 10 kg Hidróxido potásico en escamas10 kg Potassium hydroxide in flakes
- --
- 605 litros de agua605 liters of water
Se mantiene la mezcla durante 24 horas a 85ºC borboteando aire en la solución. Una vez terminada la reacción se separan los sólidos por decantación durante 6 h. Mientras se deja enfriar la reacción.The mixture is maintained for 24 hours at 85 ° C. bubbling air into the solution. Once the reaction is over Solids are separated by decantation for 6 h. While leaving cool the reaction.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
Etapa 2Stage 2
- --
- Al producto anterior conteniendo los ácidos húmicos oxidados se le añaden despacio 125 kg de citrato de hierro (III).To the previous product containing oxidized humic acids will slowly add 125 kg of iron citrate (III).
- --
- Se mantiene agitando a temperatura ambiente durante 6 hBe keep stirring at room temperature for 6 h
- --
- El producto final se deja decantar durante 6 h antes de envasar.He final product is left to decant for 6 h before package.
Los productos obtenidos según se describe contienen mayor número de grupos carboxílicos y fenólicos.The products obtained as described They contain a greater number of carboxylic and phenolic groups.
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Estudio del efecto de la aplicación de un complejo heteromolecular humato-citrato de hierro en plantas de pepino (variedad sensible Anico) cultivadas en un suelo básico (pH = 8.04) y calizo (% CO3= 23%).Study of the effect of the application of a iron humate-citrate heteromolecular complex in cucumber plants (Anico sensitive variety) grown in a soil basic (pH = 8.04) and limestone (% CO3 = 23%).
En este estudio, realizado en macetas, se comparó el efecto del quelato de síntesis de referencia para la corrección de la clorosis férrica (Fe-EDDHA isómero orto-orto), con el efecto del complejo heteromolecular Humato-citrato de Fe preparado según el ejemplo 1; en relación con la capacidad de estos compuestos para incrementar la absorción de hierro en plantas de pepino (v anico) sensibles a la clorosis férrica.In this study, carried out in pots, the effect of the reference synthesis chelate for the correction of iron chlorosis (Fe-EDDHA ortho-ortho isomer) was compared with the effect of the hemato-molecular complex Humato-citrate of Fe prepared according to the example one; in relation to the ability of these compounds to increase the absorption of iron in cucumber plants ( v anico ) sensitive to iron chlorosis.
Los resultados obtenidos después de 30 días de cultivo se presentan en la figura siguiente, en la que el quelato Fe-EDDHA isómero orto-orto se denomina (o,o) y el complejo heteromolecular (H-Cit). Las dosis de Fe aplicadas fueron: 4 ppm (o,o), y 4 y 8 ppm (H-Cit).The results obtained after 30 days of culture are presented in the following figure, in which the chelate Fe-EDDHA ortho-ortho isomer is called (or, or) and the heteromolecular complex (H-Cit). Fe doses applied were: 4 ppm (o, o), and 4 and 8 ppm (H-Cit).
Como se puede constatar en la figura 1, todos los tratamientos llevaron consigo un incremento de aproximadamente un 50% en el contenido foliar de Fe, no existiendo diferencias significativas entre el tratamiento (o,o) y el complejo heteromolecular H-Cit objeto de la invención.As can be seen in figure 1, all the treatments led to an increase of approximately 50% in the foliar content of Faith, there are no differences significant between the treatment (or, or) and the complex H-Cit heteromolecular object of the invention.
\vskip1.000000\baselineskip\ vskip1.000000 \ baselineskip
En este estudio se investigó el efecto del complejo heteromolecular humato-citrato de Fe sobre árboles de nectarina cultivados en un suelo básico y calizo. Este efecto se comparó con el efecto de un quelato de referencia Fe EDDHA. Este ensayo se realizó en un campo de alto poder olorosante en el que no se observa respuesta clara al quelato de Fe estandar (Fe-EDDHA).In this study the effect of hemato-molecular complex Humato-citrate of Fe on Nectarine trees grown in a basic and limestone soil. This effect was compared with the effect of a reference chelate Fe EDDHA This test was performed in a field of high odorous power in which there is no clear response to the standard Che chelate (Fe-EDDHA).
Los resultados obtenidos se recogen en las tablas siguientes:The results obtained are included in the following tables:
En relación con el grado de la clorosis evaluado por el color verde de las hojas, se observa que los valores mas elevados corresponden al tratamiento con el complejo heteromolecular humato-citrato de Fe objeto de la invención y preparado según el ejemplo 1 (Tabla 1).In relation to the degree of chlorosis evaluated by the green color of the leaves, it is observed that the values more elevated correspond to the treatment with the heteromolecular complex Fe humate citrate object of the invention and prepared according to example 1 (Table 1).
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\newpage\ newpage
En la tabla 2, se recogen los resultados referentes a la cosecha obtenida:Table 2 shows the results. concerning the harvest obtained:
Como se puede observar, los tratamientos con el complejo heteromolecular objeto de la invención causó incrementos muy significativos de la cosecha y calidad del fruto.As you can see, the treatments with the heteromolecular complex object of the invention caused increases Very significant harvest and fruit quality.
Claims (23)
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES200800449A ES2335562B2 (en) | 2007-03-07 | 2008-02-19 | HETEROMOLECULAR METALIC COMPLEXES (CHELATES) OF HUMAN NATURE. |
| EG2008030371A EG25629A (en) | 2007-03-07 | 2008-03-05 | Heteromolecular metal-humic 'chelate' complexes |
| PL08380068T PL1997793T5 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| CA2624735A CA2624735C (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| PT08380068T PT1997793E (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| MA30718A MA32037B1 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal complexes (chelates) of a humic nature. |
| US12/074,732 US7947818B2 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| EP08380068.0A EP1997793B2 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| SI200830800T SI1997793T1 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular metal-humic (chelate) complexes |
| DK08380068.0T DK1997793T3 (en) | 2007-03-07 | 2008-03-06 | Heteromolecular Metal-Humic Acid Complexes (Chelates) |
| BRPI0800372-6A BRPI0800372A2 (en) | 2007-03-07 | 2008-03-06 | heteromolecular metal complexes (chelates) |
| HRP20120872TT HRP20120872T4 (en) | 2007-03-07 | 2012-10-30 | Heteromolecular metal-humic (chelate) complexes |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES200700595A ES2322005B1 (en) | 2007-03-07 | 2007-03-07 | HETEROMOLECULAR METALIC COMPLEXES (CHELATES) OF HUMAN NATURE. |
| ES200800449A ES2335562B2 (en) | 2007-03-07 | 2008-02-19 | HETEROMOLECULAR METALIC COMPLEXES (CHELATES) OF HUMAN NATURE. |
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| Publication Number | Publication Date |
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| ES2335562A1 true ES2335562A1 (en) | 2010-03-29 |
| ES2335562B2 ES2335562B2 (en) | 2011-11-30 |
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| ES200800449A Active ES2335562B2 (en) | 2007-03-07 | 2008-02-19 | HETEROMOLECULAR METALIC COMPLEXES (CHELATES) OF HUMAN NATURE. |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US7947818B2 (en) |
| EP (1) | EP1997793B2 (en) |
| BR (1) | BRPI0800372A2 (en) |
| CA (1) | CA2624735C (en) |
| DK (1) | DK1997793T3 (en) |
| EG (1) | EG25629A (en) |
| ES (1) | ES2335562B2 (en) |
| HR (1) | HRP20120872T4 (en) |
| MA (1) | MA32037B1 (en) |
| PL (1) | PL1997793T5 (en) |
| PT (1) | PT1997793E (en) |
| SI (1) | SI1997793T1 (en) |
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| FR2936932B1 (en) | 2008-10-15 | 2012-08-31 | Timac Agro Int | METAL COMPLEXES; THEIR USE FOR THE PREPARATION OF COMPOSITIONS FOR AGRICULTURAL USE. |
| US8753566B1 (en) | 2009-01-09 | 2014-06-17 | Stephen R. Temple | Method for treating condensed vapor streams containing odorous compounds |
| FR2941589A1 (en) * | 2009-02-03 | 2010-08-06 | Pierre Philippe Claude | USE OF CHITINE FOR BACTERIAL BIOFERTILIZATION OF NON-LEGUMINOUS CULTURES |
| WO2011092574A1 (en) * | 2010-01-27 | 2011-08-04 | Bijam Biosciences Private Limited | A method of producing functionally effective organically chelated micronutrients |
| RU2458930C1 (en) * | 2010-12-13 | 2012-08-20 | Федеральное государственное образовательное учреждение высшего профессионального образования "Кубанский государственный аграрный университет" | Method of producing humin-containing iron chelate |
| CN102408257B (en) * | 2011-08-08 | 2013-04-10 | 山东省农业科学院农业资源与环境研究所 | Microelement-introducing weathered coal activating agent as well as activation method and application |
| CN102925161B (en) * | 2012-01-18 | 2015-04-08 | 云南省烟草公司昭通市公司 | Broad spectrum heavy metal activity deactivator preparation method |
| WO2014004582A1 (en) | 2012-06-28 | 2014-01-03 | Steen Research, Llc | Methods and equipment for treatment of odorous gas streams from industrial plants |
| CA2898872C (en) | 2013-01-22 | 2019-04-09 | Steen Research, Llc | Methods and equipment for treatment of odorous gas streams |
| CN103708909A (en) * | 2013-12-06 | 2014-04-09 | 广西科技大学 | Chitin compound fertilizer |
| RU2552064C1 (en) * | 2014-02-10 | 2015-06-10 | Общество с ограниченной ответственностью "БИО-АГРО" | Bacterial fertiliser |
| US9850179B2 (en) * | 2014-09-04 | 2017-12-26 | The Andersons, Inc. | Granular humate for spray application and process of making same |
| CN104774106B (en) * | 2015-04-08 | 2017-07-28 | 山东农业大学 | A kind of preparation method and application of chaetomium globosum bio-bacterial manure granule |
| CN104774105B (en) * | 2015-04-08 | 2017-07-28 | 山东农业大学 | A kind of preparation method and application of chaetomium globosum bio-bacterial manure pulvis |
| MX2018013612A (en) * | 2016-05-10 | 2019-03-14 | Actagro Llc | Semi-humic composition and methods of use thereof. |
| WO2018035165A1 (en) | 2016-08-15 | 2018-02-22 | Steen Research, Llc | Processes for removing a nitrogen-based compound from a gas or liquid stream to produce a nitrogen-based product |
| WO2018138642A1 (en) * | 2017-01-12 | 2018-08-02 | Agri Tech World S.R.L | Nutraceutical compositions for plants and method for their preparation |
| CN107141125A (en) * | 2017-06-23 | 2017-09-08 | 湖南锦里正稻生态农业有限公司 | A kind of paddy rice fertilizer special for organic |
| IT201700096929A1 (en) * | 2017-08-29 | 2019-03-01 | Mim82 S R L | FORMULATIONS FOR FERTILIZING ACTIVITIES |
| CN110092697A (en) * | 2019-06-04 | 2019-08-06 | 金正大生态工程集团股份有限公司 | A kind of preparation method of the acidic soil conditioner containing fulvo acid |
| MX2022002382A (en) | 2019-08-28 | 2022-03-17 | Steen Res Llc | Methods for absorbing a targeted compound from a gas stream for subsequent processing or use. |
| CN111116260B (en) * | 2020-01-03 | 2021-09-10 | 浙江丰瑜生态科技股份有限公司 | Water-soluble fertilizer containing humic acid and preparation method thereof |
| CN111233550B (en) * | 2020-01-19 | 2021-11-23 | 浙江丰瑜生态科技股份有限公司 | Humic acid water-soluble fertilizer suitable for hickory planting and preparation method and application thereof |
| CN111233573B (en) * | 2020-01-19 | 2021-11-30 | 浙江丰瑜生态科技股份有限公司 | Newly-reclaimed rice field soil improvement humic acid compound fertilizer and preparation method thereof |
| CN111217651B (en) * | 2020-02-13 | 2021-11-30 | 浙江丰瑜生态科技股份有限公司 | Humic acid-containing water-soluble fertilizer suitable for grapes and preparation method and use method thereof |
| CN111393668B (en) * | 2020-04-03 | 2022-05-20 | 太原师范学院 | Preparation method of nano hollow shell fertilizer slow release agent |
| CN111682229B (en) * | 2020-06-24 | 2022-07-15 | 中国海洋大学 | Humic acid-Fe composite modified anode, preparation method and application thereof, and seabed microbial fuel cell |
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- 2008-03-06 PL PL08380068T patent/PL1997793T5/en unknown
- 2008-03-06 CA CA2624735A patent/CA2624735C/en active Active
- 2008-03-06 BR BRPI0800372-6A patent/BRPI0800372A2/en not_active Application Discontinuation
- 2008-03-06 SI SI200830800T patent/SI1997793T1/en unknown
- 2008-03-06 PT PT08380068T patent/PT1997793E/en unknown
- 2008-03-06 DK DK08380068.0T patent/DK1997793T3/en active
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Also Published As
| Publication number | Publication date |
|---|---|
| US20080221314A1 (en) | 2008-09-11 |
| EP1997793A2 (en) | 2008-12-03 |
| SI1997793T1 (en) | 2012-12-31 |
| HRP20120872T4 (en) | 2020-10-02 |
| ES2335562B2 (en) | 2011-11-30 |
| PL1997793T3 (en) | 2012-12-31 |
| EP1997793B1 (en) | 2012-08-01 |
| EP1997793A3 (en) | 2009-02-25 |
| HRP20120872T1 (en) | 2012-11-30 |
| EG25629A (en) | 2012-04-10 |
| US7947818B2 (en) | 2011-05-24 |
| MA32037B1 (en) | 2011-02-01 |
| CA2624735A1 (en) | 2008-09-07 |
| DK1997793T3 (en) | 2012-11-12 |
| EP1997793B2 (en) | 2020-02-19 |
| BRPI0800372A2 (en) | 2008-12-02 |
| PL1997793T5 (en) | 2020-10-05 |
| PT1997793E (en) | 2012-11-14 |
| CA2624735C (en) | 2012-09-18 |
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